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以N-苯基马来酰亚胺(NPMI)和4-乙烯基吡啶-醋酸锌配合物(4VP-Zn(Ac)2)为单体,用可逆断裂链转移聚合(RAFT)方法合成了两亲性聚(N-苯基马来酰亚胺)-b-聚(4-乙烯基吡啶)-ZnS(PNPMI-b-P4VP-ZnS)高分子纳米复合物(PNCs),用核磁共振(NMR)、X射线衍射(XRD)、扫描电镜(SEM)和透射电镜(TEM)等对产物进行了表征。随着RAFT嵌段聚合时间由1 h增加到30 h,PNPMI-b-P4VP-ZnS中ZnS的质量分数由8.2%提高到12.6%,ZnS粒径由3 nm增大到200 nm,并由立方向六方晶型转变,复合物中PNPMI-b-P4VP的荧光强度逐渐下降,而ZnS的荧光强度逐渐增大。研究表明,RAFT方法可有效调控PNPMI-b-P4VP和ZnS之间的荧光共振能量转移。PNPMI-b-P4VP-ZnS在生物研究领域具有潜在的应用价值。

The amphipathic poly(N-phenylmaleimide)-b-poly(4-vinylpyridine)-zinc acetate(PNPMI-b-P4VP-Zn(Ac)2) complex has been synthesized by reversible addition fragmentation chain transfer(RAFT) polymerization,using N-phenylmaleimide and 4-vinylpyridine-zinc acetate(4VP-Zn(Ac)2) as monomers.The products as prepared have been characterized by nuclear magnetic resonance spectrum(NMR),X-ray diffraction(XRD),scanning electron microscope(SEM) and transmission electron microscope(TEM).The ZnS mass fraction increases from 8.2% to 12.6% with the block copolymerization time increasing from 1h to 30h.The particle size of ZnS also increases from 3 nm to 200 nm,accompanied with the crystal style conversion of ZnS from cubic to hexagonal.The photoluminescence(PL) intensity of PNPMI-b-P4VP decreases with the increasing block copolymerization time,however,the PL intensity of ZnS increases.Results show that,the fluorescence resonance energy transfer properties between PNPMI-b-P4VP and ZnS are controllable by RAFT method.The PNPMI-b-P4VP-ZnS FRET probe shows a potential application in the biologic field.

参考文献

[1] Ren Q;Jiang BB;Zhang DL;Yu Q;Fang JB;Yang Y;Chen JH .Studies on the atom transfer radical polymerization of a maleimide AB* monomer and modification of the halogen end groups[J].European Polymer Journal,2005(11):2742-2752.
[2] Zhai TY;Gu ZJ;Ma Y;Yang WS;Zhao LY;Yao JN .Synthesis of ordered ZnS nanotubes by MOCVD-template method[J].Materials Chemistry and Physics,2006(2/3):281-284.
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